CN118547402B - Para-aramid spinning oil and preparation method thereof - Google Patents

Abstract

The invention discloses a para-aramid spinning oil and a preparation method thereof, and belongs to the technical field of spinning oil. The invention prepares the para-aramid spinning oil with smoothing agent, emulsifier, antistatic agent, clustering agent, preservative and bactericidal agent, defoaming agent and long carbon chain silane coupling agent modified graphene oxide as raw materials. The use of synthetic ester smoothing agent can significantly improve the penetration wettability and oil film strength of the oil on aramid fiber filaments, and effectively solves the problems of lint, broken ends and poor unwinding performance in the production process. Long carbon chain silane coupling agent modified graphene oxide can not only play the role of surfactant and improve the stability of emulsion; but also can give full play to the advantage of low friction coefficient of graphene oxide, so that the filament bundle has good smoothness when in contact with metal, reduces the friction resistance between the filament bundle and the metal during high-speed operation, avoids the generation of lint and broken ends, and reduces the wear on the equipment.

Description

Para-aramid spinning oil and preparation method thereof

Technical Field

The invention belongs to the technical field of spinning oils, and in particular relates to a para-aramid spinning oil and a preparation method thereof.

Background Art

Chemical synthetic fibers are high molecular weight compounds directly polymerized from compounds. Static electricity will be generated during the spinning process. Additives are used to eliminate static electricity accumulation and make the fibers soft and smooth. Such additives are collectively called spinning oils. Spinning oils should have the following characteristics: smooth fiber surface, reduce static electricity, have clustering or cohesion effects; high thermal stability, low volatility; no corrosion to metals; good washability, no effect on fiber color; easy to mix and use, easy to obtain raw materials, and reasonable cost. The oil film protects the fiber and gives it a certain smoothness, which can reduce fiber damage during friction and give it a good feel.

Since the oil used in spinning is usually an oil-in-water emulsion, a surfactant must be used as an emulsifier, and the spinning oil must also be able to make the fiber have good antistatic properties. The raw materials used for chemical fiber oils are generally smoothing agents, emulsifiers, and antistatic agents. Other ingredients can also be added according to the different uses of the fiber. When preparing oils, relying on only a single surfactant cannot meet the needs of all aspects. According to the specific characteristics of different fibers and the specific requirements for the performance of the oil in the spinning process, different types and models of surfactants must be combined in a certain proportion to prepare qualified oil products.

Para-aramid is an aromatic polyamide fiber made by spinning poly(p-phenylene terephthalamide). Para-aramid has the advantages of high strength, high modulus, flame retardancy, high temperature resistance, and good dimensional stability. It is widely used in aviation, national defense, communications, transportation, personal protection and other fields, and is an important high-performance synthetic fiber. In the production process of para-aramid, the amount of oil used is not large, but it has a vital influence on the performance of the fiber. Its main function is to reduce the friction resistance between the fiber and the equipment, eliminate static electricity, increase the cohesion of the tow, and improve the subsequent application and processing performance of the fiber. At present, there are technical problems such as large friction coefficient with metal, unstable emulsion and poor antistatic performance during the use of oil, which limits its mass production.

Summary of the invention

In view of the problems existing in the prior art, the present invention provides a para-aramid spinning oil and a preparation method thereof.

One of the purposes of the present invention is to provide a para-aramid spinning oil, which comprises the following components in parts by weight:

40-60 parts of smoothing agent, 10-20 parts of emulsifier, 4-8 parts of antistatic agent, 5-10 parts of sizing agent, 0.5-2 parts of preservative and bactericidal agent, 0.1-1 parts of defoaming agent, 3-6 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating for reaction, centrifugal separation, washing, drying, and grinding to obtain the modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1: (0.2-0.8).

Although the prior art with authorization announcement numbers CN115287784B and CN115434044B also involves using graphene-based substances to improve the performance of spinning fibers, their preparation processes are complex and difficult to promote and use; and the emulsion prepared therefrom has poor stability and cannot effectively reduce the friction coefficient of the fiber. The present invention uses long carbon chain silane coupling agent modified graphene oxide as a spinning oil additive to better improve the stability of the emulsion and improve the lubricity of the spinning fiber.

Compared with graphene, graphene oxide has more surface active groups and better hydrophilicity. Graphene oxide has an extremely low friction coefficient and is a common lubricating material. However, when graphene oxide is added to the spinning oil alone, the stability of the emulsion will be destroyed, resulting in stratification or precipitation. Although common short-chain silane coupling agents can improve the dispersibility of graphene oxide to a certain extent, their dispersibility is poor and the performance improvement is limited. Long straight carbon chain silane coupling agents have strong lipophilicity due to their longer hydrocarbon chain segments.

The use of long carbon chain silane coupling agent to modify graphene oxide can not only improve the dispersibility of graphene oxide, but also make the modified graphene oxide have both hydrophilic graphene oxide end and lipophilic long carbon chain coupling agent end, so that it plays the role of surfactant and improves the stability of the emulsion. The hydrophilic group at one end of graphene oxide is larger, the lipophilic group at the long carbon chain end is smaller, and the internal space steric hindrance of the colloid particle is smaller, which can form smaller colloid particles, greatly improving the dispersibility and stability of the emulsion. The modified graphene oxide in the oil can form an interface film on the outer layer of the fiber, and the modified graphene oxide on the interface film forms a directional arrangement, with the hydrophilic end of the graphene oxide facing the air and the hydrophobic end facing the fiber. This arrangement allows the graphene oxide to directly contact the metal, giving full play to the advantages of the low friction coefficient of graphene oxide, and greatly improving the friction resistance of the fiber. At the same time, graphene oxide contains more active groups, which can form hydrogen bonds or chemical bonds with the amide groups on the aramid fiber, and has the technical effect of anti-dripping. The prepared spinning oil is more suitable for aramid fiber.

In some embodiments of the present invention, the synthetic ester is selected from one or more of pentaerythritol oleate, diisooctyl sebacate, isooctyl oleate, oleyl glyceride, and isooctyl stearate. Compared with alcohol ethers, esters have a larger hydrophobic group due to the double bond, which can reduce the cloud point and surface tension, increase the wetting speed, and facilitate the purpose of rapid and uniform oiling.

In some embodiments of the present invention, the synthetic ester is pentaerythritol oleate and isooctyl stearate, and the mass ratio thereof is 1:1.

In some embodiments of the present invention, the emulsifier is selected from one or more of isomeric decanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, and castor oil polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate. The use of polyether emulsifier is conducive to the dispersion of graphene oxide and reduces the friction coefficient.

In some embodiments of the present invention, the sizing agent is selected from one or more of coconut oleic acid diethanolamide, oleic acid triethanolamine, and lauroyl diethanolamide.

In some embodiments of the present invention, the defoaming agent is tributyl phosphate. The preservative and bactericide is one or more of methyl parahydroxybenzoate, ethyl parahydroxybenzoate, benzamidazole, butyl carbamate, and sodium benzoate.

In some embodiments of the present invention, the long carbon chain silane coupling agent is selected from one or more of decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane (also known as n-decyltrimethoxysilane, n-decyltriethoxysilane, n-undecyltrimethoxysilane, n-undecyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-tridecyltrimethoxysilane, n-tridecyltriethoxysilane, n-tetradecyltrimethoxysilane, n-tetradecyltriethoxysilane, n-pentadecyltrimethoxysilane, and n-pentadecyltriethoxysilane). The above coupling agents are all common long straight carbon chain silane coupling agents in the art, and have excellent modification effects. Further, the long carbon chain silane coupling agent is a mixture of dodecyltrimethoxysilane and dodecyltriethoxysilane, and the mass ratio of the two is 1:1.

In some embodiments of the present invention, the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:(200-600); the volume ratio of deionized water and ethanol in the mixed solution is 1:1; and the heating reaction temperature is 50-70°C.

In some embodiments of the present invention, the mass ratio of the graphene oxide to the long carbon chain silane coupling agent is 1: (0.3-0.6). Within this range, the graphene oxide is well modified, and the technical effects of dispersibility and emulsification can be taken into account. When the amount of long carbon chain silane coupling agent is too small, the modification is insufficient and the dispersion is poor; when the amount is too large, the long carbon chains are entangled with each other, which is not only not conducive to the dispersion of graphene oxide, but also easily leads to instability of the emulsion and stratification.

The present invention also provides a method for preparing a para-aramid spinning oil, comprising the following steps: adding each component into a reaction kettle according to a proportion, heating to 40-50° C., stirring for 1-2 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Beneficial technical effects of the present invention: The present invention uses synthetic ester as a lubricant, and adds long-chain silane coupling agent to modify graphene oxide to prepare para-aramid spinning oil. The synthetic ester lubricant in the spinning oil can significantly improve the penetration wettability of the oil on the fiber filaments and the oil film strength, and effectively reduce the problems of lint, broken ends and poor unwinding performance during the production process. The use of long-chain silane coupling agent can make it play the role of a surfactant and improve the stability of the emulsion; the modified graphene oxide in the oil can form an interface film on the outer layer of the fiber, give full play to the advantages of low friction coefficient of graphene oxide, and greatly improve the friction resistance of the fiber. The prepared para-aramid spinning oil not only has antistatic properties, but also gives the fiber a lower dynamic friction between the wire and the metal during high-speed spinning, so that the filament bundle has good smoothness when in contact with the metal, reduces the friction resistance between the filament bundle and the metal during high-speed operation, avoids the generation of lint and broken ends, and reduces wear on the equipment. At the same time, the para-aramid spinning oil also gives the fiber a higher static friction between the fibers, so that the fibers have a good cohesion and create good conditions for the smooth progress of the elastic deformation process.

DETAILED DESCRIPTION

To make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the art without making creative work are within the scope of protection of the present invention. The raw materials in the embodiments and comparative examples are all commercially available. Unless otherwise specified, the raw material types in the embodiments and comparative examples are consistent.

Example 1: Para-aramid spinning oil, in parts by weight, comprises the following components:

40 parts of smoothing agent, 10 parts of emulsifier, 4 parts of antistatic agent, 5 parts of clustering agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 3 parts of modified graphene oxide; the smoothing agent is synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating for reaction, centrifugal separation, washing, drying, and grinding to obtain the modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.3.

The synthetic ester is selected from 20 parts of pentaerythritol oleate and 20 parts of diisooctyl sebacate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from coconut oil diethanolamide; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from decyltrimethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 50°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 40° C., stirring for 2 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 2: Para-aramid spinning oil, in parts by weight, comprises the following components:

60 parts of smoothing agent, 20 parts of emulsifier, 8 parts of antistatic agent, 10 parts of bundling agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent and 6 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is as follows: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating for reaction, centrifugal separation, washing, drying and grinding to obtain the modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.6.

The synthetic ester is selected from 40 parts of diisooctyl sebacate and 20 parts of isooctyl oleate; the emulsifier is selected from isomeric tridecanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from undecyltrimethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 70°C.

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 50° C., stirring for 1 hour, cooling, and discharging to obtain the para-aramid spinning oil.

Example 3: Para-aramid spinning oil, in parts by weight, comprises the following components:

40 parts of smoothing agent, 20 parts of emulsifier, 8 parts of antistatic agent, 5 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent and 6 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is as follows: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating for reaction, centrifugal separation, washing, drying and grinding to obtain the modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.6.

The synthetic ester is selected from 10 parts of diisooctyl sebacate and 30 parts of oleyl glyceride; the emulsifier is selected from castor oil polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from 2 parts of triethanolamine oleate and 3 parts of lauroyl diethanolamine; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from tridecyltrimethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; and the heating reaction temperature is 60°C.

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 42° C., stirring for 1.3 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 4: Para-aramid spinning oil, in parts by weight, comprises the following components:

60 parts of smoothing agent, 10 parts of emulsifier, 4 parts of antistatic agent, 5 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 3 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.3;

The synthetic ester is selected from 20 parts of pentaerythritol oleate and 40 parts of oleic acid glyceride; the emulsifier is selected from 5 parts of isomeric decanol polyoxyethylene ether and 5 parts of isomeric tridecanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from tetradecyl triethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 65°C.

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 45° C., stirring for 1.7 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 5: Para-aramid spinning oil, in parts by weight, comprises the following components:

42 parts of smoothing agent, 18 parts of emulsifier, 5 parts of antistatic agent, 6 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 4 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating for reaction, centrifugal separation, washing, drying, and grinding to obtain the modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 10 parts of pentaerythritol oleate, 10 parts of diisooctyl sebacate, and 22 parts of isooctyl oleate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from coconut oil diethanolamide; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from pentadecyl triethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 58°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.8 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 6: Para-aramid spinning oil, in parts by weight, comprises the following components:

56 parts of smoothing agent, 13 parts of emulsifier, 7 parts of antistatic agent, 8 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, and 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating for reaction, centrifugal separation, washing, drying, and grinding to obtain the modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.4;

The synthetic ester is selected from 20 parts of isooctyl oleate and 36 parts of oleic acid glyceride; the emulsifier is selected from isomeric tridecanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from 4 parts of triethanolamine oleate and 4 parts of lauroyl diethanolamine; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyl triethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 65°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 47° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 7: Para-aramid spinning oil, in parts by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 8: Para-aramid spinning oil, in parts by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from pentaerythritol oleate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 9: Para-aramid spinning oil, comprising the following components in parts by weight:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 10: Para-aramid spinning oil, in parts by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.2;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 11: Para-aramid spinning oil, in parts by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.8;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 12: Para-aramid spinning oil, comprising the following components in parts by weight:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltrimethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Example 13: Para-aramid spinning oil, comprising the following components in parts by weight:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyl triethoxysilane and dodecyl trimethoxysilane, and the weight ratio of the two is 1:1; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Comparative Example 1: Para-aramid spinning oil, calculated by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene; the smoothing agent is synthetic ester; the preparation process of the modified graphene is: dispersing graphene in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain the modified graphene; the mass ratio of graphene to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Comparative Example 2: Para-aramid spinning oil, calculated by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 5 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a short carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to short carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoamer is tributyl phosphate; the short carbon chain silane coupling agent is selected from butyl triethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Comparative Example 3: Para-aramid spinning oil, calculated by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 1 part of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Comparative Example 4: Para-aramid spinning oil, calculated by weight, comprises the following components:

50 parts of smoothing agent, 15 parts of emulsifier, 6 parts of antistatic agent, 7 parts of sizing agent, 1 part of preservative and bactericidal agent, 0.5 parts of defoaming agent, 9 parts of modified graphene oxide; the smoothing agent is a synthetic ester; the preparation process of the modified graphene oxide is: dispersing graphene oxide in a solution, then adding a long carbon chain silane coupling agent, heating reaction, centrifugal separation, washing, drying, grinding to obtain modified graphene oxide; the mass ratio of graphene oxide to the long carbon chain silane coupling agent is 1:0.5;

The synthetic ester is selected from 25 parts of pentaerythritol oleate and 25 parts of isooctyl stearate; the emulsifier is selected from isomeric decanol polyoxyethylene ether; the antistatic agent is potassium dodecyl phosphate; the sizing agent is selected from triethanolamine oleate; the preservative and bactericidal agent is sodium benzoate; the defoaming agent is tributyl phosphate; the long carbon chain silane coupling agent is selected from dodecyltriethoxysilane; the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1:400; the volume ratio of deionized water and ethanol in the mixed solution is 1:1; the heating reaction temperature is 60°C;

The preparation method of the para-aramid spinning oil comprises the following steps: adding each component into a reaction kettle according to a proportion, heating to 46° C., stirring for 1.6 hours, cooling, and discharging to obtain the para-aramid spinning oil.

Performance Testing:

The para-aramid spinning oil prepared in the examples and comparative examples was prepared into a 10% emulsion, and placed at 25° C. for 7 days to observe whether precipitation or stratification occurred.

The para-aramid spinning oil prepared in the examples and comparative examples was formulated into an emulsion and used for preparing para-aramid spinning fibers. The dynamic friction coefficient between the oil-containing fiber and the metal was measured using a yarn friction coefficient tester; and the specific resistance of the oil-containing fiber was tested using a fiber specific resistance meter.

Table 1: Performance test results of para-aramid spinning oils prepared in Examples 1 to 6

Table 2: Performance test results of para-aramid spinning oils prepared in Examples 7 to 13

Table 3: Performance test results of para-aramid spinning oils prepared in Comparative Examples 1 to 4

It can be seen from Examples 1-11 that the present invention uses synthetic ester as a lubricant, and adds a long carbon chain silane coupling agent to modify the para-aramid spinning oil prepared by graphene oxide. The long carbon chain silane coupling agent can make it play the role of a surfactant, give full play to the advantages of low friction coefficient of graphene oxide, and greatly improve the friction resistance and antistatic properties of the fiber. Further, it can be seen from Examples 7-13 that when the two lubricants of pentaerythritol oleate and isooctyl stearate are compounded, it is more conducive to improving the friction coefficient of the spinning fiber; this may be because pentaerythritol oleate and isooctyl stearate have long branched chains and long straight chain structures, which can form an entanglement effect with the long carbon chain silane coupling agent and improve the dispersibility of the emulsion. Dodecyl triethoxysilane and dodecyl trimethoxysilane are compounded, and the coupling agent contains triethoxy and trimethoxy at the same time, which can play the role of "claw group" and improve the dispersion stability of graphene oxide. When preparing long carbon chain silane coupling agent modified graphene oxide, the best effect is achieved when the mass ratio of graphene oxide to long carbon chain silane coupling agent is 1: (0.3-0.6). Too little long carbon chain silane coupling agent is not conducive to the modification of graphene oxide; too much long carbon chain silane coupling agent is not conducive to the dispersion stability of the emulsion system, affecting the improvement of comprehensive performance.

Compared with Example 7 to Example 11, the performance of Comparative Examples 1 to 4 is greatly reduced. It can be seen that the use of ordinary graphene or short carbon chain silane coupling agent cannot make the modified carbon material play the role of surfactant, which affects its dispersion in the emulsion and is not conducive to reducing the friction coefficient. At the same time, the amount of modified graphene oxide as an additive should be controlled: when the amount added is too little, the graphene oxide and the long chain groups are too dispersed, unable to form a friction interface, and easy to settle, which leads to reduced friction performance; when the amount added is too much, the surface active groups of graphene oxide and the long carbon chains are entangled with each other, which easily leads to the occurrence of agglomeration, which is not conducive to improving the comprehensive performance of the spinning oil.

Claims (8)

1. The para-aramid spinning oil is characterized by comprising the following components in parts by weight:

40-60 parts of a smoothing agent, 10-20 parts of an emulsifying agent, 4-8 parts of an antistatic agent, 5-10 parts of a bundling agent, 0.5-2 parts of an antiseptic bactericide, 0.1-1 part of a defoaming agent and 3-6 parts of modified graphene oxide; the smoothing agent is synthetic ester;

The preparation process of the modified graphene oxide comprises the following steps: dispersing graphene oxide in a solution, adding a long carbon chain silane coupling agent, heating for reaction, centrifugally separating, washing, drying and grinding to obtain modified graphene oxide; the mass ratio of the graphene oxide to the long carbon chain silane coupling agent is 1: (0.3-0.6);

The long carbon chain silane coupling agent is selected from one or more of decyl trimethoxy silane, decyl triethoxy silane, undecyl trimethoxy silane, undecyl triethoxy silane, dodecyl trimethoxy silane, dodecyl triethoxy silane, tridecyl trimethoxy silane, tridecyl triethoxy silane, tetradecyl trimethoxy silane, tetradecyl triethoxy silane, pentadecyl trimethoxy silane and pentadecyl triethoxy silane.

2. The para-aramid spin finish of claim 1 wherein the synthetic ester is selected from one or more of pentaerythritol oleate, diisooctyl sebacate, isooctyl oleate, glycerol oleate, isooctyl stearate.

3. The para-aramid spinning oil according to claim 1, wherein the synthetic ester is pentaerythritol oleate and isooctyl stearate, and the mass ratio of the synthetic ester to the isooctyl stearate is 1:1.

4. The para-aramid spinning oil according to claim 1, wherein the emulsifier is one or more selected from the group consisting of isomeric deca-alcohol polyoxyethylene ethers, isomeric tridecanol polyoxyethylene ethers, castor oil polyoxyethylene ethers; the antistatic agent is dodecyl phosphate potassium salt.

5. The para-aramid spin finish of claim 1 wherein the bundling agent is selected from one or more of coconut diethanolamide, triethanolamine oleate, lauroyl diethanolamide.

6. The para-aramid spin finish of claim 1 wherein the defoamer is tributyl phosphate.

7. The para-aramid spinning finish according to claim 1, wherein the solution is a mixed solution of deionized water and ethanol; the mass ratio of graphene oxide to the mixed solution is 1: (200-600); the volume ratio of deionized water to ethanol in the mixed solution is 1:1, a step of; the heating reaction temperature is 50-70 ℃.

8. The method for preparing the para-aramid spinning finish according to any one of claims 1 to 7, comprising the steps of: adding the components into a reaction kettle according to the proportion, heating to 40-50 ℃, stirring for 1-2h, cooling, and discharging to obtain the para-aramid spinning oiling agent.